EP0019097A1 - Verfahren zur Herstellung von Methacrylatharz mit hoher Sonnenstrahlenenergie-Absorption - Google Patents

Verfahren zur Herstellung von Methacrylatharz mit hoher Sonnenstrahlenenergie-Absorption Download PDF

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Publication number
EP0019097A1
EP0019097A1 EP80102114A EP80102114A EP0019097A1 EP 0019097 A1 EP0019097 A1 EP 0019097A1 EP 80102114 A EP80102114 A EP 80102114A EP 80102114 A EP80102114 A EP 80102114A EP 0019097 A1 EP0019097 A1 EP 0019097A1
Authority
EP
European Patent Office
Prior art keywords
acid
radiant energy
methacrylic resin
solar radiant
energy absorbing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP80102114A
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English (en)
French (fr)
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EP0019097B1 (de
Inventor
Kazumasa Kamada
Yoshio Nakai
Kazunori Abe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of EP0019097A1 publication Critical patent/EP0019097A1/de
Application granted granted Critical
Publication of EP0019097B1 publication Critical patent/EP0019097B1/de
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids

Definitions

  • This invention relates to a novel methacrylic resin having a high solar radiant energy absorbing property and a process for producing the same. More specifically this invention relates to a methacrylic resin shaped article having a high solar radiant energy absorbing property and containing an organic compound containing cupric ion and a compound having at least one P-O-H bond in a molecule and a process for producing the same by polymerizing a polymerizable unsaturated monomer having methyl methacrylate as a main component in the presence of an organic compound containing cupric ion and a compound having at least P-O-H bond in a molecule.
  • a methacrylic resin has an excellent transparency and weather-ability. Therefore it has come to be used for so-called grazing uses such as windows, ceiling windows, doors of buildings and vehicles. But it has a defect that its transmission of solar radians energy is so high that, for example, in case it is exposed to the direct sunshine, the internal temperature rise will be noticeable.
  • a resin is called to have a high solar radiant energy absorbing property, when it absorbs comparatively much of the solar radiant energy in spite of high visible light transmission.
  • the spectral distribution of the solar radiant energy and the relative luminous efficiency are mentioned in various literature. For example, in JIS R3208 "Heat Ray Absorbing Glass", the spectral distribution of the solar radiant energy and the relative luminous efficiency are described in detail. According to the spectral distribution of the solar radiant energy by JIS R3208, more than 80% of the solar radiant energy is occupied by the rays in the wave length range of 400 to 1,100 nm (nanometers). From the relative luminous efficiency defined in JIS R3208, it is found that the visible light transmission is determined substantially by the transmission of the light in the wave length range of 500 to 650 nm.
  • the light in the wave length range longer than 1,100 nm are absorbed somewhat strongly by polymethyl methacrylate and that the light in the wave length range shorter than 400 nm can be substantially absorbed by adding a marketed ultraviolet light absorbent properly into a methacrylic resin
  • the resin article By adding into a resin a marketed yellow dye suitably, we can make it possible for the resin article to absorb selectively and strongly the light in the wavelength range of 400 to 500 nm.
  • the resin will be unavoidably colored yellow, or if any other colored substance is present, a color combined with it. Therefore, only in case the yellowing of the resin is not unsuitable, it will be a desirable method to obtain a resin of a low transmission of the light in the wave length range of 400 to 500 nm by suitably adding a yellow dye into the resin article.
  • the solar radiant energy absorbing property will not be sufficient in practical use.
  • the subject matter of the present invention is a methacrylic resin having a high solar radiant energy absorbing property wherein an organic compound (A) containing cupric ion in an amount of 0.01 to 5 parts by weight calculated as cupric ion and a compound (B) having at least one P-O-H bond in a molecule in an amount to be 0.1 to 10 mols per mol of the above mentioned organic compound (A) are contained per 100 parts by weight of a methacrylic resin selected from homopolymers of methyl methacrylate or copolymers of polymerizable unsaturated monomer mixture containing at least 50% by weight of a methyl methacrylate and a process for producing methacrylic resin having a high solar radient energy absorbing property which comprises polymerizing a polymerizable material selected from methyl methacrylate or a polymerizable unsaturated monomer mixture containing at least 50% by weight of methyl methacrylate or- its partially polymerized product, including an organic compound (A)
  • the methacrylic resin having a high solar radiant energy absorbing property according to the present invention can be obtained by any process, it is desirable to obtain the above mentioned composition by a bulk polymerization or preferably a mold polymerization.
  • the polymerizable raw material to be used in the production of the resin of the present invention is methyl methacrylate alone or a polymerizable unsaturated monomer mixture containing at least 50% by weight of methyl methacrylate or its pertially polymerized product.
  • (meth)acrylic acid meaning acrylic acid or methacrylic acid here and hereinafter
  • esters of (meth)acrylic acid and alcohol represented by methyl acrylate, ethyl(meth) acrylate, butyl(meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl(meth)acrylate ethyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; (meth)acrylamide and its derivatives; s
  • a polymerizable unsaturated monomer mixture containing ar least 50% by weight of methyl methacrylate it will be more preferable to contain at least 60% by weight, or further at least 80% by weight of methyl methacrylate.
  • a mixture of 85 to 100% by weight of methyl methacrylate in this range and 0 to 15% by weight of a member selected from among methyl acrylate, ethyl acrylate, butyl acrylate, (meth) acrylic acid and 2-hydroxyethyl (meth)acrylate or a mixture of them is particularly preferable.
  • a partially polymerized product is used as a polymerizable raw material, as a preferable example for obtaining it, there is a method of obtaining the partially polymerized product which contains 5 to 35% by weight of polymers by polymerizing methyl methacrylate or the mixture of it and the other unsaturated monomers in the bulk state at boiling point of them.
  • the organic compound (A) containing cupric ion to be used in the present invention there can be enumerated salts of such carboxylic acids as formic acid, acetic acid, propionic acid, valeric acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, stearic acid, oleic acid, 2-ethylhexanoic acid, naphthenic acid and benzoic acid and cupric ion and complex salts of acetylacetone or acetoacetic acid and cupric ion.
  • carboxylic acids as formic acid, acetic acid, propionic acid, valeric acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, stearic acid, oleic acid, 2-ethylhexanoic acid, naphthenic acid and benzoic acid and cupric ion and complex salts of acetylacetone
  • the organic compound (A) containing cupric ion is added into the resin in an amount of 0.01 to 5 parts by weight calculated as cupric ion per 100 parts by weight of methyl methacrylate or a polymerizable unsaturated monomer mixture containing at least 50% by weight of methyl methacrylate or its partially polymerized product.
  • the amount of the organic compound containing cupric ion does not reach 0.01 part by weight calculated as cupric ion, the solar radiant absorbing property of the resin will not be sufficient.
  • it exceeds 5 parts by weight such physical properties as the mechanical strength of the resin will be noticeably reduce.
  • the compound (B) having at least one P-O-H bond in a molecule is added in an amount of 0.1 to 10 mols per mole of the organic compound containing cupric ion. In case it is less than 0.1 mol, the solar radiant energy absorbing property will not sufficiently improve. On the other hand, in case it exceeds 10 mols, the mechanical strength of the obtained resin material will noticeably reduce.
  • the amount of the compound having at least one P-O-H bond in a molecule may be decided by properly judging the relation between the degree of the improvement of the solar radiant energy absorbing property and other physical properties.
  • the organic compound containing cupric ion is dissolved in an unsaturated monomer having methyl methacrylate as a main component or its partially polymerized product.
  • the solubility may be insufficient depending on the kind and amount of the organic compound containing cupric ion.
  • carboxylic acids as formic acid, acetic acid, propionic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, naphthenic acid
  • additives used in producing ordinary methacrylic resin may be added.
  • additives there can be enumerated dyes and pigments used for coloring, antioxidants, such stabilizers as ultraviolet ray absorbent, flame- reterdants, plasticizers and mold releases making it easy to release the resin material from the mold.
  • an ultraviolet ray absorbent into a resin in order to prevent such deteriorations as the discoloration, crazing and skin roughening of the resin article from being caused by ultraviolet light. Further, the addition of the ultraviolet ray absorbent can reduce the solar radiation transmission without reducing the visible light transmission of resin article and is therefore preferable from the point of improving the solar radiant energy absorbing property.
  • the performances required of such ultraviolet ray absorbent to be used are to absorb fully rays in the wavelength range deteriorating the resin plate and not to react with cupric ion to form a complex hardly soluble in a polymer having methyl methacrylate unit as a main component.
  • 2-hydroxybenzophenone derivatives as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxy- benzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4,4'-dibutoxybenzo- phenone, 2-hydroxy-4,4'-dioctyloxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-methoxy-2',4'-dichlorobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone, such benzotriazole derivatives as 2-(2'-hydroxy-3',5'-ditertiarybutylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditertiarybutylphenyl)benzotriazole, 2-(2'-hydroxy
  • an ultraviolet ray absorbent it is preferable to add 0.01 to 1 part by weight of an ultraviolet ray absorbent to be used per 100 parts by weight of a polymer having methyl methacrylate unit as a main component. It is more preferable to add 0.1 to 0.5 part by weight of it.
  • the additives into the resin if a yellow dye is added, the solar radiant energy absorbing property of the resin will improve. Therefore, if in the quantitative range not obstructing the object of the present invention, it can be enumerated as an example of a preferable additive.
  • carbon black give an effect of antiglaring to the resin and has an absorption over the entire wave length range of solar radiation rays from 290 to 2,140 nm. Therefore, if carbon black is added in the method of the present invention, a resin having high antiglare property and solar radiant energy absorbing property will be obtained. Therefore, a method wherein 0.0001 to 0.05 part by weight of carbon black is added per 100 parts by weight of a polymer having methyl methacrylate unit as a main component can be enumerated as one of preferable working manners of the present invention. Therefore, they can be enumerated as examples of preferable additives within the quantitative range not obstructing the objects of the present invention.
  • such radical polymerization initiator as azo compound or an organic peroxide is preferably used by 0.0001 to 0.5 part by weight, or more preferably used by 0.001 to 0.2 part by weight per 100 parts by weight of methyl methacrylate or polymerizable unsaturated monomer mixture containing at least 50% by weight of methyl methacrylate, or its partially polymerized material.
  • azo compound used as a radical polymerization initiator there can be enumerated 2,2'-azobis (isobutylonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis(2,4-dimethyl, 4-methoxyvaleronitrile).
  • organic peroxides there can be enumerated di-tertiarybutyl peroxide, tertiarybutylcumyl peroxide, dicumyl peroxide a,a'-bis(tertiarybutylperoxide) hexane, a,a'- bis(tertiarybutylperoxy) p-isopropylbenzene, 2,5-dimethyl-2,5-di(tertiarybutylperoxy) hexane, 2,5-dimethyl-2,5-di(tertiarybutylperoxy) hexine-3, tertiarybutyl peroxyacetate, tertiarybutyl peroxyiso- butylate, tertiarybutyl peroxypivalate, tertiarybutyl-2-ethyl hexanoate, tertiarybutyl peroxylaurate, tertiary
  • radical polymerization initiators may be used alone or two or more of them may be used together.
  • organic peroxides it is preferable to add one or more of the above mentioned organic peroxides to a resin to be heat molding and it is more preferable to add 0.05 to 1 part by weight or more preferably 0.1 to 0.5 part of an organic peroxide selected from the above mentioned di-tertiarybutyl peroxide, tertiarybutylcumyl peroxide and dicumyl peroxide per 100 parts by weight of a polymer having methyl methacrylate unit as a main component.
  • polymerization is carried out at various temperature, depending on kind of the radical polymerization initiator, generally at the temperature range of 40 to 140°C. It is preferably, that the polymerization is carried out, at first at the temperature range of 40 to 90°C, and in succession at the temperature range of 100 to 140°C.
  • the thickness of the resin plate obtained by the casting polymerization is not particularly limited but is preferably the thickness of an ordinarily marketed methacrylic resin plate, that is, within the range of 1 to 65 mm.
  • Controls 1 to 4 had the amount of cupric acetate made the oxys mentioned in Table 2 and was poured into a mold in the same manner as in Example 1 to obtain a transparent resin plate of a thickness of 3 mm.
  • Example 1 a composition consisting of was poured in and otherwise the same operation as in Example 1 was repeated to obtain a light blue transparent resin plate.
  • the visible light transmission of this plates was 76.6%, and the solar radiant energy transmission of it was 62.9%, and so it had high solar radiant energy absorbing property.
  • the visible light transmission of this plate was 76.2% and the solar radiant energy transmission of it was 52.6%, and so it had a high solar radiant energy absorbing property.
  • Example 7 In the same manner as in Example 7 except that the composition to be poured in was changed to be of a light bluish green transparent plate of a thickness of 6 mm was obtained.
  • the visible light transmission of this resin plate was 77.6% and the solar radiant energy transmission of 53.5% and had a high solar radiant energy absorbing property.
  • the visible light transmission and the solar radiation transmission of these plates were the values shown in Table 3, had high solar radiant energy absorbing property and had an antiglare property.
  • the resin plate made by combining the dibutyl phosphate and cupric acetate with carbon black type pigment has a higher solar radiant energy absorbing property than the resin plate made by using the carbon black type pigment alone-.
  • Example 2 The same operation as in Example 1 was repeated except that the composition to be poured in was changed to be of to obtain a light blue transparent resin plate of thickness of 3 mm.
  • the visible light transmission of this resin plate was 79.2% and the solar radiation transmission of it was 55.7% and had a high solar radiant energy absorbing property.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
EP80102114A 1979-04-20 1980-04-18 Verfahren zur Herstellung von Methacrylatharz mit hoher Sonnenstrahlenenergie-Absorption Expired EP0019097B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP49240/79 1979-04-20
JP4924079A JPS55142045A (en) 1979-04-20 1979-04-20 Methacrylic resin material having excellent solar radiation absorptivity, and its preparation

Publications (2)

Publication Number Publication Date
EP0019097A1 true EP0019097A1 (de) 1980-11-26
EP0019097B1 EP0019097B1 (de) 1984-08-15

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EP80102114A Expired EP0019097B1 (de) 1979-04-20 1980-04-18 Verfahren zur Herstellung von Methacrylatharz mit hoher Sonnenstrahlenenergie-Absorption

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US (1) US4296214A (de)
EP (1) EP0019097B1 (de)
JP (1) JPS55142045A (de)
AU (1) AU536726B2 (de)
DE (1) DE3068938D1 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0175317A2 (de) * 1984-09-18 1986-03-26 BASF Aktiengesellschaft Verfahren zur Herstellung von Carboxylgruppen enthaltenden Polymerisaten
EP0398653A1 (de) * 1989-05-16 1990-11-22 Mitsubishi Chemical Corporation Herstellungsverfahren für hoch wasserabsorbierende Polymere
EP0454462A1 (de) * 1990-04-27 1991-10-30 Sumitomo Chemical Company, Limited Verfahren zur Herstellung von Vinylpolymer oder Vinylidenpolymer
US5185413A (en) * 1989-05-16 1993-02-09 Mitsubishi Petrochemical Company Limited Process for producing highly water-absortive polymers
EP0586135A2 (de) * 1992-08-20 1994-03-09 Kureha Kagaku Kogyo Kabushiki Kaisha Optischer Filter
US5466755A (en) * 1992-08-20 1995-11-14 Kureha, Kagaku Kogyo Kabushiki Kaisha Optical filter
EP1731571A1 (de) * 2004-03-10 2006-12-13 Kureha Corporation Lösungsvermittler und zusammensetzung damit
DE102007040258A1 (de) 2007-08-24 2009-02-26 Evonik Röhm Gmbh Lichtdurchlässiger Sonnenenergiekollektor

Families Citing this family (16)

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Publication number Priority date Publication date Assignee Title
DE3375150D1 (en) * 1982-07-30 1988-02-11 Kyowa Gas Chem Ind Co Ltd Neodymium-containing transparent resin and method for manufacture thereof
EP0147728B1 (de) * 1983-12-13 1988-08-10 Mitsubishi Rayon Co., Ltd. Methakrylsäureesterharzzusammensetzung
JPS63304044A (ja) * 1987-06-04 1988-12-12 Kurasawa Kogaku Kogyo Kk 高屈折率化メタクリル樹脂
DE4120312C1 (de) * 1991-06-20 1993-02-18 Roehm Gmbh, 6100 Darmstadt, De
JP3933215B2 (ja) * 1996-01-30 2007-06-20 株式会社クレハ 熱線吸収性複合体
TW445380B (en) * 1996-10-23 2001-07-11 Sumitomo Chemical Co Plasma display front panel
DE69817263T2 (de) * 1997-06-19 2004-07-15 Sumitomo Chemical Co., Ltd. Frontscheibe für Plasma-Anzeige
EP1008599B1 (de) 1997-08-26 2004-06-02 Kureha Kagaku Kogyo Kabushiki Kaisha Kupfer-enthaltende phosphorsäureester-derivate und verfahren zu ihrer herstellung, nahinfrarot-aborber, und im nahinfrarot absorbierende acrylharzzubereitungen
WO1999026951A1 (fr) * 1997-11-21 1999-06-03 Kureha Kagaku Kogyo Kabushiki Kaisha Compose de phosphate et de cuivre, composition contenant ce compose et produit de mise en application
WO1999026952A1 (fr) * 1997-11-21 1999-06-03 Kureha Kagaku Kogyo Kabushiki Kaisha Composes de phosphate, composes de phosphate et de cuivre et leurs procedes de preparation, substance et composition absorbant les infrarouges proches et leur produit de mise en application
JPH11160529A (ja) * 1997-11-21 1999-06-18 Kureha Chem Ind Co Ltd 光学フィルターおよびこれを備えた装置、熱線吸収フィルター、光ファイバー並びに眼鏡レンズ
DE69909345T2 (de) * 1998-02-03 2004-05-27 Nippon Shokubai Co. Ltd. Phthalocyaninverbindung, deren Herstellungsverfahren und Verwendung
JP2001097984A (ja) 1999-09-28 2001-04-10 Nisshinbo Ind Inc 近赤外吸収化合物
DE10252031A1 (de) * 2002-11-06 2004-05-27 Micronas Gmbh Vorrichtung und Verfahren zum Erfassen einer Winkelposition eines rotierenden Gegenstandes
US6710197B1 (en) * 2002-11-12 2004-03-23 Chung-Shan Institute Of Science And Technology Method for the preparation of copper (meth) acryloyloxyethyl phosphate coordination complex
SI1790701T2 (sl) * 2005-11-25 2012-05-31 Sicpa Holding Sa Ir absorbirajoča tiskarska barva za intaglio

Citations (2)

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CH463790A (de) * 1963-07-31 1968-10-15 Edison Soc Verfahren zur Polymerisation oder Copolymerisation von Vinyl- und/oder Vinylidenmonomeren und Katalysatorgemisch zur Durchführung des Verfahrens
US3647729A (en) * 1967-04-10 1972-03-07 Kyowa Gas Chem Ind Co Ltd Infrared-absorbent methyl methacrylate resin composition and shaped articles thereof

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BE566972A (de) * 1957-04-23
US3355418A (en) * 1964-12-23 1967-11-28 American Cyanamid Co Stabilization of methyl methacrylate and copolymers against discoloration with organic phosphites
FR1473094A (fr) * 1966-01-06 1967-03-17 Electrochimie Soc Procédé de polymérisation des esters acryliques et méthacryliques
JPS4844675A (de) * 1971-10-08 1973-06-27
US3950314A (en) * 1974-06-17 1976-04-13 Rohm And Haas Company Process for improving thermoformability of methyl methacrylate polymers and the improved compositions
JPS546598A (en) * 1977-06-16 1979-01-18 Nippon Bunko Kogyo Kk Apparatus for making elution for liquidchromatography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH463790A (de) * 1963-07-31 1968-10-15 Edison Soc Verfahren zur Polymerisation oder Copolymerisation von Vinyl- und/oder Vinylidenmonomeren und Katalysatorgemisch zur Durchführung des Verfahrens
US3647729A (en) * 1967-04-10 1972-03-07 Kyowa Gas Chem Ind Co Ltd Infrared-absorbent methyl methacrylate resin composition and shaped articles thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0175317A2 (de) * 1984-09-18 1986-03-26 BASF Aktiengesellschaft Verfahren zur Herstellung von Carboxylgruppen enthaltenden Polymerisaten
EP0175317A3 (en) * 1984-09-18 1987-01-28 Basf Aktiengesellschaft Process for the manufacture of polymers containing carboxylic groups
EP0398653A1 (de) * 1989-05-16 1990-11-22 Mitsubishi Chemical Corporation Herstellungsverfahren für hoch wasserabsorbierende Polymere
US5185413A (en) * 1989-05-16 1993-02-09 Mitsubishi Petrochemical Company Limited Process for producing highly water-absortive polymers
EP0454462A1 (de) * 1990-04-27 1991-10-30 Sumitomo Chemical Company, Limited Verfahren zur Herstellung von Vinylpolymer oder Vinylidenpolymer
US5153283A (en) * 1990-04-27 1992-10-06 Sumitomo Chemical Co., Ltd. Process for producing vinyl polymer or vinylidene polymer
EP0586135A2 (de) * 1992-08-20 1994-03-09 Kureha Kagaku Kogyo Kabushiki Kaisha Optischer Filter
EP0586135A3 (de) * 1992-08-20 1994-05-18 Kureha Kagaku Kogyo Kabushiki Kaisha Optischer Filter
US5466755A (en) * 1992-08-20 1995-11-14 Kureha, Kagaku Kogyo Kabushiki Kaisha Optical filter
US5567778A (en) * 1992-08-20 1996-10-22 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing an optical filter
EP1731571A1 (de) * 2004-03-10 2006-12-13 Kureha Corporation Lösungsvermittler und zusammensetzung damit
JPWO2005087870A1 (ja) * 2004-03-10 2008-01-24 株式会社クレハ 可溶化剤及びこれを含有する組成物
EP1731571A4 (de) * 2004-03-10 2011-03-02 Kureha Corp Lösungsvermittler und zusammensetzung damit
JP4926699B2 (ja) * 2004-03-10 2012-05-09 株式会社クレハ 可溶化剤及びこれを含有する組成物
DE102007040258A1 (de) 2007-08-24 2009-02-26 Evonik Röhm Gmbh Lichtdurchlässiger Sonnenenergiekollektor

Also Published As

Publication number Publication date
JPS55142045A (en) 1980-11-06
AU536726B2 (en) 1984-05-24
AU5727280A (en) 1980-10-23
DE3068938D1 (en) 1984-09-20
EP0019097B1 (de) 1984-08-15
US4296214A (en) 1981-10-20
JPS625190B2 (de) 1987-02-03

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